DE2848137C2 - Imaging material - Google Patents

Description

The invention relates to an image recording material having a substrate and one formed thereon Lead layer or layer containing lead (hereinafter referred to as "lead layer"). In particular, the invention relates to a dispersion imaging material Gradation, excellent resolution and improved shelf life.

From DE-OS 2632122 and DE-OS 2233827 image recording materials are known which have, as a photosensitive layer, a lead layer which also contains selenium or tellurium. In DE-OS 2541 083 are dispersion images materials previously described in the record layer does not contain lead, but an organic stabilizer

3ICl

\ .IIIIIUI &.

Furthermore, in JA-OS 19303/1973 an image recording material is described which has the following features, among others:

1. The image recording material comprises a substrate and a dispersion image recording layer deposited thereon which is made of a metal having a relatively low melting point, like tellurium or bismuth;

2. The image recording material is that of a xenon flash lamp or the like. exposed to emitted high energy:

3. When the metal image-recording layer of the recording material absorbs an amount of energy which is above a certain critical threshold value, the image-recording layer becomes in the energy-absorbing areas melted;

-f. the molten metal image recording layer experiences a contraction and distribution or dispersion into tiny spheres due to its surface tension:

5. the optical density of the imaging layer becomes in those areas in which the layer melted and distributed or dispersed., reduced; and

6. In this way, a different optical density results in the image recording layer between see the energy absorption areas and the areas not exposed to energy, whereby a picture emerges.

The term "dispersion" or "dispersion" refers here to the phenomenon that a coherent, thin, solid film made of a material is inaccessible It becomes coherent if, in the case of energy input, the energy absorbed in the material is a certain one exceeds critical threshold. The term "dispersion imaging layer" therefore denotes a layer of a material capable of doing so hig! is to bring about the "dispersion" defined above.

On the aforesaid image recording material, even in a light color after the drying process Space can be recorded without conventional development an image. Image recording materials of this type used in the microfilm sector, inter alia, have im Compared to conventional imaging media

Hen ζ. B. good functionality (as explained above) as well as the skills for "additional recording" and "annotation" (i.e. for recording an additional Image on the non-image areas of a material on which an image has already been created), which can be found at 5 conventional imaging materials only. difficult to realize.

However, if tellurium or bismuth, as mentioned, is used for the dispersion image recording layer of an image recording material are used, its gradation and resolution are sufficient for use in Microfilming is not off. In addition, the shelf life is insufficient, as is often the case with thin metal films is recognizable. In the present context, “storage stability” means maintaining the optical density before or after the use of the imaging material and the preservation of the sensitometric Understand material characteristics such as gradation, resolution and sensitivity. Thin metal films tend to be oxygenated by the oxygen and / or moisture in the air. The thickness of an as An image recording layer of a recording material for a metal thin film serving as a microfilm, as will be explained below, usually 20 to 200 nm, so that such a film is excellent sensitometric features (such as sensitivity, resolution or contrast) can be achieved. Metal films with the thickness range mentioned are particularly susceptible to oxidation, which is why they are caused by the oxidation not only is the optical density reduced, but also the sensitometric properties are impaired will. In the field of manufacturing electronic parts and materials, among others. toilet "already some Methods proposed by which oxidation of thin metal films prevented and sold: n films shelf life should be awarded. These methods are generally characterized by the fact that an oxidation-inhibiting Layer (anti-oxidation layer) such as a silicon oxide layer is provided. Such antioxidant layers however, usually have a considerable thickness, so that when applied to a Image recording materials tend to have the sensitometric characteristics of the recording material in spite of the improvement of the shelf life of the material. The reason for this is that the image recording function of recording materials of the type described above mainly on the Deformation (i.e. dispersion) of the imaging layer and thus the stiffness of the antioxidant layer disadvantageously suppresses this deformation of the image recording layer.

The object of the invention is therefore to provide an image recording material which has a dispersion image recording layer with improved storage stability as well as gradation and excellent resolving power without impairing the image recording power is deteriorated, as is the case with the conventional means for improving the shelf life (such as the provision of an antioxidant layer) is the case. Another task is in the To provide a method of recording an image on a having the aforesaid features Imaging material.

The following detailed description referring to the attached drawing provides more detailed information Details regarding the foregoing and other objects, as well as the features and advantages of the invention evident.

The drawing is a photomicrograph taken with a scanning electron microscope (8000x Enlargement) of a lead layer deposited on a polyester film in a vacuum. ·

As mentioned, a thin bismuth film imparts as a dispersion imaging layer almost no gradation in an image recording material; the dispersed or dispersed bismuth globules are large, resulting in poor resolving power. One can <; ine Gradation due to partial oxidation of the dispersion image-recording layer serving, thin bismuth film, but such partial oxidation is in the Unsatisfactory in terms of resolving power, since the dispersed beads are partially oxidized Bismuth differ greatly in shape from the spherical shape and have a large size. An excellent one Resolution is generally achieved when the dispersion imaging layer is used is distributed or dispersed in tiny spheres. Under "globules" are here not only particles with (exactly) spherical shape, but also those with up to a certain degree to understand deformed or deviating shapes.

According to the present invention, it has been found that by using a thin lead layer as an image recording layer, an image recording material having gradation and excellent resolving power can be obtained. Lead results in a thin film with a structure of substantially dome-shaped grains which are oriented substantially vertically to the substrate, when e.g. B. with regard to the layer carrier on which the thin BIeischk.ht is deposited, and the conditions for the deposition of the thin lead layer the right choice is made. Further, it has been found that an image recording material which has a thin lead layer having a substantially dome-shaped grain structure as an image recording layer has gradation and excellent resolving power. The expression "essentially dome-like grain structure" refers here to a collection of small grains, which are oriented essentially vertically to form a layer support, as can be seen from the drawing, which is a photomicrograph of a polyester film taken with a scanning electron microscope at 8000x magnification Vacuum-deposited layer of lead: with regard to an essentially dome-shaped grain structure see also Toshinobu Takagi "Atara shii Hyomenshori Gijutsu (New Methods for Surface Treatment)" [Tokyo: Hyomenshori Journal Co. (1974), pages 11 to 19]. The essentially dome-shaped grains of the lead layer generally have a mean surface diameter of about 0.1 to 10 mm when magnified 8000 times under the scanning electron microscope, which corresponds to an actual mean surface diameter of about 0.0125 to 1.25 μm . Such grains are often in the form of two or more interconnected grains. Because of the essentially dome-shaped grain structure, the lead layer can have the effect that, when the energy absorbed in this layer is converted into thermal energy, the heat transfer in the lateral direction of the layer is inhibited. This is believed to be the reason that such a lead layer gives gradation and that when sufficient energy is applied, the lead layer is dispersed into very small spheres, thereby improving the resolving power.
The one essentially dome-shaped grain structure

κ-containing lead layer is due to its high (specific

· "., See) surface compared to that contained in the air

■ '.,. Oxygen and / or water particularly susceptible to oxidation

£> lig, which among other things leads to a poor shelf life

i-5 leads. The one essentially dome-shaped grain

j- structure having lead layer is therefore mainly in air

'■ oxidizes quickly, especially at high humidity, and the opti-

The density of the layer is quickly reduced as a result.

: It was found to be an effective method for

i · Eliminate this instability of the lead layer in it

stands on or above the lead layer a layer of at least one element from the group indium, germanium, Apply antimony and tin. One over the lead layer Organic polymer layer located there can be provided by removing the organic polymer layer applied to the inorganic stabilizing layer deposited on the lead layer.

, / The invention is therefore an image recording

> ^: ning material with a layer support and one on top

: formed lead layer, which is characterized

is that the lead layer contains at least 20 wt .-% lead and a substantially dome-shaped grain structure produced by vacuum evaporation, sputtering or ion plating and that the image recording material also an inorganic stabilizing layer formed on the lead layer. which is at least 80% by weight of indium. Germanium, antimony. Tin or a combination contains thereof.

An inorganic stabilization layer. which contains at least one of the aforementioned four elements, can be as extremely thin as 0.5 to 30 nm. preferably 1 to 15 nm. Higher layer thicknesses lead to a decrease in sensitivity and resolution rather than an increase the shelf life. The reason for this may be that the layer of such an element itself may have the characteristics that the layer is difficult to bead up by the application of energy or is dispersible and that even in the case of a distribution of the layer with the aid of a very high amount of energy generally dispersed beads of large size result. These properties occur for example in experiments carried out on a laminate film made from a polyester film as a substrate and a layer applied to the substrate and having a considerable thickness consists of one of the elements mentioned.

Of the aforementioned four elements, which for a inorganic stabilization layer to stabilize the lead layer with a substantially dome-shaped Grain structure can be used effectively, germanium is most preferred because it has the gradation and the resolving power which can be achieved with the aid of the lead layer is not impaired. One of Reasons for this is that even a very thin Germanium layer in contrast to corresponding layers of the other elements the stability of the lead layer can improve.

One of the methods of additionally increasing bo As mentioned, the shelf life of the lead layer consists in the provision of an organic polymer = the stabilization layer over the inorganic stabilization layer. Specific examples of organic polymers, which can be used to form such an additional stabilization layer Polyvinylidene chloride. Vinylidene chloride / acrylonitrile copolymers. Polyvinyl acetate, polyvinyl cinnamate. Polyisoprene, polybutadiene, polystyrene, polymethyl methacrylate, Polyurethanes, polyvinyl butyral, epoxy resins, cellulose acetate, linear saturated polyesters, fluorine and silicone rubbers or rubbers, silicone resins and silicone varnishes. The polymers mentioned can be used individually or in a mixture can be used. If necessary, the polymers can also be used in combination in the form of a Use multiple layer. Of the organic polymers mentioned, vinylidene chloride / acrylonitrile copolymers are particularly preferred, linear saturated polyesters, fluororubbers, silicone resins and silicone varnishes. You can add a silicone oil to the organic polymer (at most about 3% by weight, based on the polymer) a crosslinking agent (at most about 20% by weight, based on the polymer), an antistatic agent (at most about 1% by weight, based on the polymer), a surface-active one Agents (at most about 1% by weight, based on the polymer), inter alia. to improve processability, the film strength and d ^ l. incorporate.

A preferred image recording material of the present invention having excellent storage stability as well as gradation and excellent resolution is thus z. B. an image recording material. which a layer support (such as a polyester film), a layer of lead applied to the layer support essentially dome or hemispherical grain structure, a germanium layer with a thickness of 2 to 8 nm and a layer of germanium applied to the lead layer the germanium layer applied layer of a linear saturated polyester with a thickness of 0.2 to 2μιη includes. »

As a support for the image recording material according to the invention For example, films made of organic polymers such as polyesters are suitable. Cellulose acetate, Nitrocellulose, polyethylene. Polypropylene. Polyvinyl chloride. Polyamide. Polymethyl methacrylate and polystyrene and sheets made of organic materials such as glass or mica. Organic polymer films are called Substrate is preferred because it enables a substantially cliff-shaped grain structure to be achieved. in the lead layer facilitate. Particularly preferred are polyester films, as these not only have a high surface smoothness, excellent heat resistance and low moisture absorption, but also good distribution which have deposition sites for gaseous lead atoms, which are then in the form of the lead layer with im essential dome-shaped grain structure are to be deposited.

In order to obtain a lead layer with an essentially dome-shaped grain structure, it is important, in addition to the type of substrate, to correctly choose the conditions for the deposition of the lead layer. Drying methods, for example, are suitable for applying the lead layer to the layer substrate. like evaporation in a vacuum, Z., sputtering ("sputtering") and ion plating. Of these methods, vacuum evaporation is preferred. When applying the lead layer, the extent of the vacuum, the temperature of the substrate and the speed of vapor deposition of the lead layer are decisive factors in achieving an essentially dome-shaped grain structure in the lead layer χ 10 " ^I0 to 1.33 χ 10" ⁵ bar, preferably 6.65 χ ΙΟ " ⁹ to 6.65 r 10 ~ ⁷ bar, the ^{substrate temperature 10 to 150 =} C. preferably 15 to 100 ^° C. and the vapor deposition rate 0.02 to 50nm / sec., Preferably 0.1 to 20nm / sec. Under these conditions, the lead

layer achieves a practically dome-shaped grain structure, resulting in gradation and high resolution.

The thickness of the lead layer is also one of the important factors that determine the gradalion. affect the resolution, among other things. In addition, the lead layer affects the optical density of the image recording material, so that it must be determined depending on the purpose of the material. If the image recording material is to be used, for example, on the microfilming box, the optical density is preferably in the range from 1 to 1.5. which corresponds to a thickness of the lead layer of about 50 to 90 ηm. The thickness of the lead layer can be varied depending on whether the layer contains one or more other elements or not. However, bet generally complains about 20 to 200 minutes. If the lead layer is too thick, the gradation and resolution tend to deteriorate. The Mindcs'.dickc ^w > ^r d hiUm'siK'htii'h ini Hinhlii'k: itif determines the contrast of an image to be generated on the recording material. The lead layer serving as the imaging layer is distinguished by this. that it gives a suitable and sufficient optical density at a thickness which provides ciradation and high resolving power.

The lead layer of the inventive image recording material may contain at least one element other than lead in addition to lead. In this sense includes the term "lead layer" in the present context is not just a layer consisting of lead alone, but also layers, which are made of lead and at least one other element in the form of a mixture, an alloy or a multilayer. In contrast, a “layer of lead” often becomes one made exclusively of lead existing layer. In a method for producing a containing at least one other element Lead layer, a lead alloy is evaporated in a vacuum and deposited on a layer support. Another method is to vaporize lead contained in a boat in a vacuum and at the same time with one or more additional element (s). that (the) is (are) present in (a) further boat, applied to a layer support. With yet another In this process, lead and at least one other element are applied to the carrier in several layers. The production of a lead layer containing at least one further element is preferably carried out in such a way that that the layer contains a lot of lead in its area adjacent to the layer support. To achieve this, if, for example, lead is first applied to the substrate, wmach the other) n) Element (s) are applied in multi-layer construction. Optionally, the first one is present in a shuttle Lead evaporated in vacuo and deposited on the substrate, and before the completion of lead evaporation one begins with at least one other element contained in a boat in a vacuum evaporate and deposit. For example, when applying an alloy, a 90 wt% lead is first used The alloy containing it is evaporated in vacuo and deposited on the substrate, after which a 50 Applying weight percent lead alloy in the same manner. By doing this, you can get an im create a substantial dome-shaped grain structure in the lead layer and thus an improvement in the gradation and the resolution. Specific examples of the lead layer of the image recording material of the present invention incorporable elements are bismuth. Indium, aluminum, tin, zinc. Antimony, selenium, Cadmium and tellurium. These elements can be used individually or in combination. Of the aforementioned Bismuth is preferred for the elements. If the bismuth content is too high, however, there is a tendency that the shelf life of the lead layer is insufficient. The aforementioned elements can be used for improvement of the sensitometric features, such as the gradation. Sensitivity and minimum optical density (O. D. ","), can be used. When used in combination the layer should contain at least 20% by weight of lead and at least one of the aforementioned elements. preferably at least 50% by weight. Contains lead, based on all elements of the lead layer. If the Lead content of the bleach layer is less than 20% by weight, there is a tendency that the gradation and resolution are poor and the storage stability is sometimes not sufficiently improved with the aid of a stabilizing layer can be.

The lead layer is often partially oxidized during and or after its deposition. As a result contains the lead layer is sometimes lead oxide. If the proportion of the lead layer is Pb in the form of lead oxide but 20% or less (expressed as an atomic percentage. based on the total lead) is the influence of lead oxide on the sensitometric characteristics small amount. D. It is also one of the favorable properties of lead as the material of the image recording layer.

On the materials of an inorganic stabilization layer to eliminate the instability of the lead layer belong - as mentioned - four elements, i.e. indium. Germanium. Antimony and tin. These elements can either individually or in combination in the form of a mixture, an alloy or a multilayer be applied. You can use any of these four elements after a drying process, such as by vapor deposition in vacuo or atomization vapor deposition (Aufsput'.crn). Apply to the bleach layer.

Of the aforementioned four elements for the inorganic Stabilizing layers tend to be indium and antimony and tin for alloying with lead. When any of these elements are deposited on the lead layer the respective alloy is therefore often formed during or after the deposition of the element. The elements for the inorganic stabilization layer probably also form an alloy with others Elements as lead, which are contained in the lead layer. The shelf life is determined by the formation of a however, such alloy is hardly affected. Ds ... image recording material according to the invention can therefore either an inorganic stabilization layer, which essentially consists of indium, germanium. Antimony, Tin or a combination thereof alone, or have an inorganic stabilizing layer, soft except indium. Germanium. Antimony, tin or a combination thereof also in the form of an alloy Contains lead and / or at least one other element that has migrated from the lead layer. That on the lead layer In addition to indium, the material to be deposited to form the inorganic stabilization layer Germanium, antimony. Tin or a combination thereof a small proportion of at least one other Elements included. Specific examples of other additional elements are lead, bismuth, aluminum, zinc, Selenium, cadmium and tellurium. In any case, it is necessary that the inorganic stabilization layer at least

80% by weight (based on all elements of the layer) of indium. Germanium, antimony, tin, or a combination of which contains.

The cause of the improvement in storage stability by any of the above four on the lead layer with a largely inactivated surface, however, it is believed. that the aforementioned four elements in each case on activating points present in the lead layer, which the essentially dome-shaped Have grain structure and are susceptible to oxidation, act and inactivate these areas and thus the lead layer with a largely inactivated surface structure by covering the surface of the blister layer equip. As mentioned, the inorganic Siabilisicrungsschicht even with very thin training an ι? Exercise excellent Stabilization Telekl, why the inactivation effect on the activated sites is presumably very large.

The four elements for the inorganic stabilizing layer can often be oxidized during or after their deposition on the lead layer. the However, the shelf life of the lead layer is not impaired by the oxidation of the respective element.

It is conceivable to provide a lead layer, which for Improvement of the shelf life in itself indium. Germanium. Contains antimony, tin, or a combination thereof. However, this cannot be done in this way Achieve sufficient support of the lead layer. It is therefore advantageous to apply the inorganic jo on the lead layer with an essentially dome-like grain structure see stabilization layer to be applied. The lead schichl can, however, improve the sensitometric Features indium, antimony. Contain tin or a combination thereof.

J5 an auxiliary stabilization layer made of the same material how to provide the inorganic stabilization layer. In this case, the auxiliary stabilization layer is applied on the substrate and the lead layer on the auxiliary layers. after which one on the lead layer -to applies a further stabilization layer, namely an inorganic stabilization layer or an inorganic one Stabilization layer with an organic stabilization layer formed thereon. In case of a A layer of lead sandwiched between two stabilizing layers can reduce the shelf life even higher than in the case in which a stabilization layer is only applied to the lead layer will. However, if an auxiliary stabilization layer is placed between the support and the lead layer the former layer occasionally tends to make the im essential dome-shaped grain structure of the lead layer to be applied to the auxiliary stabilization layer to change and thereby worsen the gradation and the resolution. Hence, the twisehen The auxiliary stabilizing layer which can be produced on the support and the lead layer is preferably of a thickness only 0.2 to 3 nm.

As mentioned, you can improve the shelf life an organic stabilization layer containing an organic polymer on the inorganic Apply stabilization layer. For this purpose, a solution of an organic polymer is preferably used applied in an organic solvent. The application can be carried out by spin coating. Rolling can be carried out, among other things. The thickness of the organic Stabilization layer (after drying) is preferably 0.1 to 5 μm, in particular 0.2 to 2 μm.

In another aspect, the invention provides a method of recording an image according to a Drying process, which consists in providing an image recording material which has a Layer support, a lead layer formed on the layer support which contains at least 20% by weight of lead, and a has a substantially dome-shaped grain structure, and an inorganic one formed on the lead layer Stabilizing layer containing at least 80% by weight of indium, germanium, antimony, tin or a combination contains thereof, and allows an amount of energy to act on the image recording material which is sufficient for the energy absorbed in the lead layer or the lead layer and the inorganic stabilization layer above a certain critical threshold to increase the optical density in the of the energy to reduce exposed areas.

One can set a certain critical threshold exceeding energy in a predetermined pattern on an image recording material according to the invention ~ 'Let it work for the creation of the image. For this purpose, for example, one can use a suitably contrasted Use an image-bearing mask. The mask is brought into close contact with the imaging material and allows energy to act on the recording material through the mask to produce the image to transfer the recording material. Radiation energy is preferably used as the energy for the image transmission applied with a short pulse width. Various types of radiation energy sources can be used Use flash lamps; a xenon flash lamp is preferably used. The pulse width of one Energy emitted by the flash lamp can be set to a millisecond or less, which is what the invention provides is preferred. Suitable as masks with sufficient resistance to such energy e.g. chrome masks. Metal niasques. Dry silver film masks and Diazofilmm.isken. Such masks can be a continuous tone or gray scale image exhibit.

As types of energy which the image recording material according to the invention IR rays emitted by an infrared lamp, for example, are also suitable. Laser beams, electron beams, or those transmitted by direct application of a heater Thermal energy. At times, the energy can be applied to the image recording material of the present invention without using it can be fed directly to a mask. Where the image recording material according to the invention is energy is supplied in such a way that the layer of the metallic element is melted and dispersed a very good image can be recorded on the material.

The image recording material of the present invention can be used as a microfilm in the form of a roll or a card as a copy film, a film for making a printing plate or used as a material for making a printed circuit board.

The invention will now be explained in more detail by the following examples. The ones described in the examples Properties are measured and evaluated using the following methods:

1. Optical density (O.D.):

The optical density is produced with the help of a according to the regulations of ASA-PH 2.19-1959 Densitometer determined.

2. Reduction of the optical density:

The reduction in optical density is calculated using the following equation:

OD after storage
of the image recording

Reduction of materials

optical density = 100-

(O. D.) in% O.D. immediately after

χ 100

Manufacture of the imaging material

Gradation:

A dry silver salt type photosensitive film mask. on which the image of a eight-step wedge was photographed, is brought into close contact with an image recording material. At the picture of the step wedge the optical density changes gradually for the determination of the gradation. The üi! Daü!> 'C; calculation material is exposed to a blit / of 600 V of a xenon flash lamp through the mask. the Lamp has a pulse width of 50 microseconds and a capacitor capacity of 120 μF and is placed at a distance of 10 mm from the surface of the image recording material.

The optical densities in all stages of the image recording material! transferred step wedge image are plotted graphically in relation to the optical densities in the corresponding steps of the step wedge image pholographierien on the mask, the ordinate representing the optical density of the image on the image recording material and the abscissa the optical density of the image on the mask. The gradation is determined on the basis of the slope of the straight line in the graphical representation. The slope is referred to as the »■ / value«. The lower the - / - value is. the higher the gradation.
Resolving power:

A diazo film mask. on which a 1010 resolution tert-diagram photographed according to NBS is in close contact with an image recording material brought. The imaging material is flash exposed through the mask. The image obtained is viewed through an optical one Microscope and determines the resolution.

Shelf life:

An image recording material is stored in a relative Thermohygrosuu held at 6O ⁰ C and 70% humidity. The shelf life is determined on the basis of the time-related reduction in the optical density and changes in gradation and resolving power.

The following examples are intended to explain the invention in more detail; however, they are not in the limiting sense To understand sense, via numerous modifications and further embodiments are possible.

Example 1 and Comparative Example I.

A 75 nm thick film of lead is made according to the method of vapor deposition in vacuo under the following conditions on a ΙΟΟμηι thick polyester film:

99.999 wt%

Lead purity:

Evaporation Ship Material

chens:

Distance between shuttle and

Polyester film:

Temperature of the Polye.ster film:

Degree of vacuum:

Disposal speed:

Tantalum

20 cm

30 C

2.66 χ ΙΟ " ⁸ bar

0.? nm sec.

The one as lead schich! serve '.' · '7 ^ nm gap film of lead has an optical density of 1.3 and, when viewed with a scanning electron microscope, an im essential dome-shaped grain structure. The material obtained (Bildaufnahmnuiterial 1) with the has a layer of lead applied to the polishing film excellent sensilometric properties, i.e. one / Value of 3.5 and a resolution of ISO lines mm. However, the recording material has one Poor storage stability: after storage for one hour at 60'C and 70'N relative humidity, the optical density by 75%.

After storage under the above conditions, the - / - value and the resolution of the image recording material * 1 cannot be measured. The measurements are therefore carried out when the reduction in optical density after storage for 20 minutes at 60 ° C. and 70% relative humidity amounts to 20%. The v-value is S and the resolution is 100 lines mm.
Furthermore, a 75 nm thick film of lead is applied in the manner described above to a 100 μm thick polyester film. A 5 nm thick film of germanium (purity: 99.999% by weight) as an inorganic stabilizing layer is then applied to this film by the vacuum evaporation method using a tantalum boat for the Ge to be evaporated. Image recording material 2 is thus obtained.

A 6% by weight is then applied to each of the vapor-deposited layers of the image recording materials 1 and 2 ige ethoxyethyl acetate solution of a linear saturated polyester by the spin coating method applied and then dried. In this way, the polyester layers each having a 0.5 μm thick layer are obtained Image recording materials 3 or 4. The properties of the image recording materials are then determined

Table I.

Image recording material

before storage

after storage

Resolution (lines / mm) reduction rune
the OD (%)

resolution
(Lines / mm)

3 Yes 3.0 200 10 3.5 180 T
£. no 3.5 180 6th 3.5 180 4th Yes 3.0 200 4th 3.0 200

near: Table I shows the results. The shelf life is after 7 days of storage at 60 ° C and 70% relative humidity determined.

Comparative example 2

A 36 nm thick bismuth film is applied by the vacuum vapor deposition method under the following conditions ΙΟΟμπι thick polyester film applied:

Purity of bismuth: 99.99 wt% Evaporation ship material chens: tungsten Distance between shuttle and Polyester film: 20 cm Temperature of the polyester film: 25 ^C C Degree of vacuum: 2.66 χ 10 " ⁸ bar Deposition speed: 0.5 nm, sec.

The 3ό nm thick bismuth film has an optical uichia of 1.35 and, when viewed with the aid of the scanning electron microscope used in Example 1, does not show an essentially dome-shaped grain structure. The image recording material obtained with the bismuth layer vapor-deposited on the polyester film has poor sensitometric properties, ie a y value of 25 and a resolution of 70 lines / mm. The decrease in optical density after 7 days storage at 6O ⁰ C and 70% relative humidity beträet 35%.

The same polyester solution as in Example 1 is then applied to the vapor-deposited bismuth layer of the material after the spin coating method and dried. This gives an image recording material with a 0.5 µm thick polyester layer. The image recording material comprising the polyester layer has a y value of 20 and a resolution of 80 lines / mm. After 7 days of storage at 60 ° C. and 70% relative humidity, the reduction in optical density is 28%.

In addition, a 6 nm thick germanium film is made according to Example 1 applied to the vapor-deposited bismuth layer of the material. The one obtained in this way Image recording material having a germanium layer

'.5 material has a resolution of 50 lines / mm. The decrease in optical density after 7 days storage at 60 ⁰ C and 70% relative humidity is 25%.

Example 2

Image recording media according to Example 1 are prepared. except that indium, antimony or tin are used as the element of the inorganic stabilization layer instead of germanium. The image recording materials are then each provided with essentially the same polyester layer as in Example 1. The properties of the image recording materials are then determined; Table II shows the results. The storage stabilities are determined after 7 days storage at 60 ⁼ C and 70% relative humidity.

Table II

Element of the stabilization layer Thickness of the stabilization layer (A)

before storage after storage

Resolution (lines mm) decrease
the OD (%)

Resolution (lines, mm)

in iOO 3.5 ItK: O τ rv
J. \ J 150 Sb 60 3.0 200 6th 3.0 180 Sn 100 3.5 180 6th 3.0 160

Example 3

45

Image recording materials are prepared according to Example 1. except that the thickness of the germanium layer serving as the inorganic stabilizing layer is changed. Instead of a linear unsaturated polyester layer, the recording materials are each provided with a 0.6 μm thick layer of a fluororubber. The fluororubber solution used for spin coating has the following composition: Fluororubber:
Crosslinking agent:
Methyl ethyl ketone:
Ethoxyethyl acetate:

5% by weight 0.25% by weight 44.75% by weight 50% by weight

Determining the characteristics of the Bildaufze. "'Planning materials. Wherein are obtained as shown in Table III the results. The storage stabilities are determined after 7 days storage at 6O ⁰ C and 70% relative humidity.

Table III before the storage after storage 7th resolution
(Lines / mm) Thickness of the
Germanium layer
nm x 10 "' V resolution
(Lines / mm) reduction
the OD (%) 2.5
3.0
3.5
6.0 150
200
160
130 15th
40
100
200 3.0
3.0
4.0
6.0 180
200
160
130 10
5
3
7th

Example 4

An image recording material is produced with the aid of a semicontinuously operating device for vacuum vapor deposition and atomization vapor deposition ("sputtering"), which has a film unwinding device and a film winding device. In this device there is a vacuum evaporation zone and a sputter evaporation zone close to a water-cooled roller. In the vacuum evaporation zone, a lead (degree of purity: 99.999% by weight) containing molybdenum boat is attached at a distance of 15 cm from the surface of the water-cooled roller. In the sputtering evaporation zone there is a germanium target, which is connected to a water-cooled plate and surrounded by a shell with a hole for the introduction of argon. The device is pumped empty with the help of a pump system to a vacuum of about 1.33 10 " ⁸ bar, after which the atomization vaporization zone is again filled with argon to a vacuum of about 6.65 χ ίθ ~ ⁶ bar. At this vacuum in the Zerstäubungsbedampfungszone is the vacuum in the Vakuumaufdampfzone about 1.33 χ 10 ~ ⁷ bar.

A 125 μm thick polyester film provided as a layer support is then moved at a speed of 1 m / min, from the unwinding roll to the water-cooled one RoHe 7'ir take-up roll. In the vacuum evaporation zone lead is vapor-deposited onto the polyester film, creating a layer of lead. The deposition or The vapor deposition rate of the lead is 10 nm / sec. The thickness of the lead layer is 70 nm Lead vapor deposition increases the surface temperature of the polyester film to 70 to 80 ° C. In the atomization evaporation zone Germanium is applied to the lead layer of the vaporized lead using the »RF sputtering method« Polyester film that has left the vacuum evaporation zone. upset. It forms an as Inorganic stabilization layer serving germanium layer with a thickness of 40 nm Lead layer provided with a germanium layer shows when viewed with the same scanning electron microscope as in Example 1, an essentially dome-shaped one Grain structure. The grains of the structure are smaller than those of the structure of the material of Example i.

Two types of organic polymer solutions are then rolled onto the wound film. First a solution of IO wt .-% of a linear unsaturated polyester and 0.1 wt .-% silicone oil in one Solvent gcmisdi from ethoxyethyl acetate and cyclohexanone (Weight ratio 80:20) applied to the germanium layer and dried. You get a polyester layer with a dry thickness of 0.4μπι. Then a 3 wt .-% solution of a Silicone resin in n-heptane is applied to the polyester layer and dried, leaving a silicone resin layer with a dry density of 0.2 μm.

The properties of the image recording material obtained are determined and receives the following results:

Maximum optical density (OD "" _v ) = 1.4:
r = 3

Resolution = 220 lines / mm

Storage stability (after 1 month of storage at 60 ^° C and 70% pure liver moisture):
Reduction animal OD = 4%

Resolution:

not changed significantly
not changed significantly

Using a laser beam point with a diameter of 2 μm or a thermal head (thermal head) of 10 μπι χ 100 μπι is on the image recording material recorded a clear picture.

Example 5

A 50 nm thick film of lead is applied to a 100 μm thick polyester film using the vacuum vapor deposition method. A 15 nm thick bismuth film is then applied to the lead layer by the vacuum vapor deposition method and a 7 nm thick germanium film is then applied to the bismuth layer, likewise by the vacuum vapor deposition method. The deposition conditions essentially correspond to those of Example 1.
When viewed with the same scanning electron microscope as in Example 1, the deposited (composite) layer of Biei shows. Bismuth and germanium have a substantially dome-shaped grain structure in which the grains are relatively large.
The same polyester solution as in the example is then applied to the deposited layer by the centrifugal coating method. and dried. An image recording material with a 0.3 μm thick polyester slide is obtained. This image recording material has a value of 2.5 and a resolution of 180 lines / mm. The image recording material was left for 7 days at 60 ° C. and 70% relative humidity, after which the reduction in optical density was 10% and the · / value was 2.0. The resolution was not significantly changed by storage.

Furthermore, an image recording material essentially corresponding to the above is produced in an analogous manner Imaging material in which only a 65 nm thick layer of lead replaces the Lead layer and bismuth layer occurs. The image recording material having the bismuth layer possesses a better sensitivity than the image recording material without a bismuth layer.

. Example 6

A vacuum is applied at a vacuum of 2.66 χ lü ~ ⁸ bar using three boats, which lead. Containing cadmium or germanium. A measuring or control instrument for determining the thickness of a vapor-deposited film is attached above each boat. A 100μπι thick polyester film is arranged at a distance of 20 cm from the boat in question. Between the polyester film and the three boats! each has a lock. During the vacuum evaporation, the polyester film has a temperature of 30 ° C. and is allowed to rotate in a horizontal plane.

The boat containing the lead and the boat containing the cadmium are heated and the closure above the boat containing the lead is opened to deposit lead on the polyester film until the measuring instrument shows a thickness of the vapor-deposited lead film of 15 nm.
Then the closure above the boat containing the cadmium is opened in order to deposit cadmium on the vapor-deposited lead film at the same time as lead. The vapor deposition is carried out at such a rate that the lead and cadmium in the case of a

Individual deposition each at a speed of 1 nm / sec. would be deposited. If both the measuring instrument above the boat containing the lead as well as the measuring instrument above the the cadmium-containing boat indicates a vapor-deposited film thickness of 30 nm, one closes the closure above the boat containing the lead and then separates on the vapor-deposited Lead / cadmium film covers a 10 nm thick film of cadmium alone. Then you close the lock ίο above the boat containing the cadmium, heats the boat containing the germanium and opens the closure above the boat containing the germanium in order to deposit germanium on the vapor-deposited cadmium film until the measuring device has a Indicates thickness of deposited germanium film of 5nm. On the deposited germanium film is then, as in Example 3, the same fluororubber solution as in Example 1 was applied and dried to obtain an image recording material. The fat the fluororubber layer is 0.6 μπ ;.

The properties of the image recording material obtained were determined, whereby the following results were obtained achieved:

25th

V = 2.5

Resolution = 180 lines / mm

Storage stability (after 7 days of storage at 60 ° C and 70% relative humidity):

8th%

Decrease in O. D.

7 = 3

Resolution = 160 lines / mm.

35

Example 7

Vacuum deposition is carried out under essentially the same conditions as in Example I. by. A 1 nm thick germanium film is applied as an auxiliary stabilization layer to a 125 μm thick polyester film. A 30 nm thick film is then placed thereon deposited from lead, on this a 25 nm thick bismuth film is applied and on this in turn deposited a 5 nm thick germanium film as an inorganic stabilization layer.

Then a 7 wt .-% solution of a vinylidene chloride / acrylonitrile copolymer in a solution Medium mixture of methyl ethyl ketone / ethoxy ethyl acetate (weight ratio 50:50) applied to the vapor-deposited layer by the spin coating method and dried. An image recording material is obtained with a 0.8 μm thick layer of vinylj- 5; denchloride / acrylonitrile copolymers. .

The properties of the image recording material obtained were determined, whereby the following results were obtained achieved:

OD «, - 1.25 ^w

V = 2.5

Resolution = 180 lines / mm

Reduction of the OD (relative to lOtägiger storage at 6O ⁰ C and 70% humidity) = 5%. "

Furthermore, an image recording material is presented in practically the same way as before, except that no auxiliary stabilization layer is applied. One be corrects the properties of the image recording material obtained and achieves the following results:

y = 2

Resolution = 180 lines / mm

Reduction of the O. D. (after 10 days of storage at 60 ° C and 70% relative humidity) = 8%.

In addition, an image recording material is placed in practically the same way as before, except that the auxiliary stabilization layer is used instead of the 1 nm thick Germanium film applies a 4 nm thick germanium film. When determining the properties of the image recording material, the following results are obtained:

7 = 5

Resolution = 140 lines / mm

Reduction of the O. D. (after 10 days of storage at 60 ° C and 70% relative humidity) = 4%.

Example 8

Under essentially the same vacuum evaporation conditions as in Example 1, a 2 nm thick indium film is applied to a 125 μm thick polyester film, then an 80 nm thick film of lead and finally a 5 nm thick indium film on this. The vapor-deposited film is then coated with the same polyester solution as in Example 1 by the spin-coating method. After drying, an image recording material with a 1.2 μm thick polyester layer is obtained. The properties of the image recording material are determined and the following results are obtained:

OD _m " _A = 1.4

y = 3

Resolution = 160 lines / mm

Reduction of the OD (relative to 2-week storage at 6O ⁰ C and 70% humidity) = 6%.

Example9

You make a lead / bismuth alloy and put it in a boat. The alloy is then made from the Vaporized boat and applied to a ΙΟΟμπι thick polyester film, a lOOnm thick film is formed, which consists essentially of 80 wt .-% Pb and 20 Wt% Bi. The vacuum evaporation conditions are as follows:

Temperature of the polyester film: Degree of vacuum: Evaporation rate:

4O ⁰ C

2.66 χ ΙΟ " ⁷ 1 nm / sec.

It is then applied to the vapor-deposited lead / bismuth film under practically the same conditions as previously applied a 5 nm thick germanium film.

The same polyester solution as in Example 1 is then applied to the vapor-deposited film by the spin-coating method and dried. An image recording material with a 0.6 μm thick polyester layer is obtained. The properties of the imaging paint are determined. where one achieved the following results:

O ₁ D ..., - 1.1

Resolution = 180 lines / mm

Reduction of the OD (relative after 7 days storage at 60 ⁰ C and 70% humidity) = 12%.

Example 10 and Comparative Example 3

Vacuum evaporation is carried out at a vacuum of 2.66 10 ~ ⁸ bar using a boat containing lead and a boat containing antimony. The lead and antimony are simultaneously vapor-deposited onto a 100 μm thick polyester film held at 30 ° C. at a rate such that the lead in the case of individual deposition at a rate of 1 nm / sec. and the antimony in the case of single deposition at a rate of 0.1 nm / sec. were deposited. The image recording material obtained has a 77 nm thick lead / antimony layer deposited on the polyester film. If this image recording material is stored for 7 days at 60 ° C. and 70% relative humidity, the reduction in optical density is then 20%.

In addition, a 10 nm thick film is formed on the vapor deposited layer of the above image recording material applied from antimony alone. In the case of this recording material is the reduction in optical density after 7 days of storage at 60 ° C and 70% relative humidity 8%.

On the antimony film of an image recording material of the type described immediately above is then the same solution of the vinylidene chloride / acrylonyl copolymer as in Example 7 by the spin coating method upset. Natt. Drying received an image recording material with a 0.7 µm thick layer of the copolymer. Man Lv diminishes the properties this imaging material, whereby the following results are obtained:

7 = 3

Resolution = 160 lines / mm

Reduction of the OD (relative after 7 days storage at 6O ⁰ C and 70% humidity) = 5%.

Example 11 and Comparative Example 4

Under the following vacuum vapor deposition conditions, lead is first applied to a 100 μm thick polyester film applied, after which bismuth is deposited on the bidding layer:

Temperature of the polyester film:
Degree of vacuum:
Evaporation rate:

40 ° C

6.65 xlO " ⁸
1 nm / sec.

After the bismuth evaporation is deposited on the Bismuth film according to Example 1 additionally applied a 5 nm thick germanium film. Afterward becomes the same solution of vinylidene chloride / acrylonitrile copolymer as in Example 7 by the spin coating method applied to the deposited germanium film. An image recording material is obtained with aΟ.Η.μπι thick layer of vinylidene chloride / acrylonitrile copolymers.

Thereafter, three image recording materials were prepared according to the methods described above. welehe differ in terms of the proportion of lead to the total amount of lead and bismuth. Man determines the properties of the imaging materials, achieving those shown in Table IV Results. The shelf life is determined after storage for 7 days at 60 ° C. and 70% relative humidity.

Table IV

Image recording
material
1
2
3 Blcianteil ' 60
30th
10 ,. before the %) storage 2.0
5.0
10.0 resolution
(Lines / mm)
160
130
100 after storage ·) Lead bond ■ = - ^ - Xx 11.34 OD
1.35
1.30
1.30 reduction
the OD {%)
12th
16
30th

where .V is the thickness (nm) of the deposited B-soap film and Y is the thickness (nm) of the deposited bismuth film.

55

When the image recording characteristics are observed with the same scanning electron microscope as in Example 1, it is found that the image recording material 1 has a substantially dome-shaped grain structure with such relatively large grains, the image recording material 2 has a substantially dome-shaped grain structure with relatively small grains, and the image recording material 3 has none have a substantially dome-shaped grain structure.

Example 12
Analogously to Example 3, essentially dicsi-1-bcn image recording materials with a 4 nm thick germanium layer are produced as in Example 3 mentioned, except that the thickness of the fluororubber layer is changed. The thickness of the fluororubber layer is adjusted by varying the amount of the solvent mixture used in the formulation of Example 3. The properties of the image recording materials obtained were determined, the results shown in Table V being obtained. The shelf life is determined after storage for 7 days at 60 ° C. and 70% relative humidity.

21

Table V

before storage after storage

Fluororubber layer thickness (μΐπ) 1.0 2.0 4.0

■ / resolution (lines / mm) 3.0

3.5

5.0 Vertninderune of the O. D. (%)

- 4th
3

Example 13 and Comparative Example 5

You make an antimony / bismuth alloy and put it in a boat. Then essentially According to Example 1, a 70 nm thick Fflm made of lead is applied to a 100 μm thick polyester film, after which the Sb / Bi alloy from the boat is deposited onto the lead film.

In the manner described above, two image recording materials are then prepared which are mutually exclusive differ with regard to the antimony content of the alloy layer. One uses for the two image recording materials two different compositions of Sb / Bi alloys. You then determine the properties of the image recording materials, the results shown in Table VI being obtained. the Storage stability is determined after storage for 7 days at 60ΝΓ and 70% relative humidity.

Table IV Layer thickness
(nm) before storage Resolution (lines / mm) after storage Sb / Bi alloy layer 8th
12th V 200
180 Decrease in O.D. (%) Antimony content (wt%) (nm) 3.0
2.5 12th
20th 90
60

Claims (1)

Patent claims: 1. Image recording material with a substrate and a lead layer formed thereon or Lead-containing layer, characterized in that the layer is at least 20 wt .-% Contains lead and has a substantially dome-shaped grain structure, which is formed by vapor deposition in the Vacuum, sputter evaporation or ion plating has been generated, and that the image recording material further has an inorganic stabilizing layer formed on the layer which contains at least 80% by weight of indium. Contains germanium, antimony, tin or a combination thereof, having. 2. Bildaufnahmmaierial according to claim 1, characterized in that on the inorganic Stabilization layer also an organic stabilization layer which contains an organic polymer is formed. ι D: i * i _ .. r, r - ι « _A _ :. i t. λ li I ₉ . -r. utiuauii.wn.iiiiuiigaiiiaLCi lai tiavn miapi uui ι uuci 2, characterized in that the support is a film made of an organic polymer. 4. Image recording material according to one of claims 1 to 3, characterized in that the Lead layer or lead-containing layer has a thickness of 20 to 200 nm. 5. Image recording material according to one of claims 1 to 4, characterized in that the inorganic stabilization layer has a thickness of 0.S to 30 nm. 6. Image recording material according to one of claims 1 to S. characterized in that the inorganic stabilizing layer consists of a) indium. Germanium. Antimony. Tin or a combination thereof and b) lead. Bismuth. Aluminum. Zinc. Selenium. Cadmium, tellurium, or a combination thereof consists. 7. Bildaufzciichnungsmaterial according to any one of claims I to 6, characterized in that the Layer of the organic polymer at least one vinylidene chloride / acrylonitrile copolymer, a linearly saturated polyester, a fluororubber Contains silicone resin or a silicone varnish. 8. Image recording material according to one of claims 1 to 7, characterized in that the Layer of the organic polymer has a thickness of 0.1 to 5 μm. 9. Image recording material according to one of claims I to 8, characterized in that the lead containing layer consists essentially of lead. 10. Bildaufnahmmalerial according to any one of claims 1 to 8, characterized in that the Lead-containing layer of lead and bismuth. Consists of indium, aluminum, tin, zinc, antimony, selenium, cadmium, tellurium, or a combination thereof. 11. Image recording material according to one of the Claims 1 to IQ, characterized in that there is also one between the layer support and the Lead layer or lead-containing layer contains formed auxiliary stabilization layer, which at least 80 wt .-% of iridium. Contains germanium, antimony, tin, or a combination thereof. 12. The image recording material of claim 11. characterized in that the auxiliary stabilization layer has a thickness of 0.7 to 30 nm.